Production of skeletonized low reflectance glass surface with fluosilicic acid vapor



July 13, 1-948.

Filed oct. a, 1946 COPPE l JA PRODUCTION 'oF sx GLAss SURFACE WITH F H. NICOLL LETONIZED LOW REFLECTANGE LUOS $111 CIC AC ID VAPOR ETAL 6 Sheets-Sheet 1 JLU 3 ent Imran/f HMM?? "s Fad E. Imlfmf l8r v A Gttomeg July 13, 1948.

Filed oct. a, 194e F. H. NICOLL ET AL PRODUCTION 0F sKELE'roNIzED Low REFLECTANGE GLASS SURFACE vwrm FLUosILICIc ACID VAPOR 6 Sheets-Sheet 2 JW. /cA /w/Mafl? KJ) Assay /M/f. (aux 7W! .4 Paire)V HLM.: .snow aarrfo uns. Mawr 20% a/v 77M! Ava/Rss.

p4 r4 f90/w 2% /f/w 6am;

Gttorneg July 13, 1948- F. H. NlcoLl. ET Al. 2,445,238

PRODUCTION OF SKELETONZED LOW REFLECTANCE GLASS SURFACE WITH FLUOSILICIC ACID VAPOR Filed Oct. 8, 1946 6 Sheets-Sheet 3 PAQl/f' OBJECT CMM@ Gtorneg July 13, 1948- F. H. NlcoLl. ETAL 2,445,238

PRODUCTION OF SKELETONIZED LOW REFLECTANCE GLASS SURFACE WITH FLUOSILICIG ACID VAPOR Filed Oct. 8, 1946 6 Sheets-Sheet 4 4 man ma .fa sa 2a fo .5 3 z f w/vWr/Mr/a/v of' @2x41 75) l l0 ffy/PHP4 70H5 (056MB @mmf/M05) 55 .50 50 z5 20 f5 l0 5 0 zooo ' ifffcr of rfMPf'iAraRf 0,1/ 77M' 77,145 aF rifnrMfA/r of yPE 5 3.5 6M. snow w75 @A4553 foon aaa

3.7 32 J3 ,I4 J5 .16 3.7

July 13; 1948 F. H. NlcoLL ETAL 2,445,238

PRODUCTION 0F SKEIJETONIZED LO' REFLECTNGE GLASS SURFACE '1TH FLUOSILIGIC ACID VAPOR Filed Oct, 8, 1946 6 Sheets-Sheet 5 /M/vfff MMD/mr:

l/ f1; f4 :AMPLI a 15% #zag .MMPzfo x57; aan@ sa i0 l fro/vars [MRD/YEL? #6M Ji@ ,40050 Pfl Ml. -Milf/dll Sgnentors Frederzcl: E Nico/ t e Fard L Wlzidmf n ttorneg July 13, 1948. F. H. NlcoLl. ETAL 2,445,238 y PRODUGTION 0F SKLETONIZED LOW REFLECTANCE GLASS' SURFACE '1TH FLUOSILICIC ACID VAPOR v Filed Oct; 8, 1946 6 Sheets-Sheet 6 Bmxntors [bede-rick Il Mcall d Fard E. llmd a. Gttomeg A Patented July 13, 1948 PRODUCTION F SKELETONIZED LOW RE- FLECTANCE GLASS SURFACE WITH FLUO- SILICIC ACID VAPOR Frederick H. Nicoll and Ferd E. Williams, Princeton, N. J., asslgnors to Radio Corporation of America, a corporation of Delaware Application October 8, 1946, Serial No. 701,902

- 7 Claims. 1

This application is a continuation-impart of an application of Nicoll and Williams, Serial No. 488,938, filed May 28, 1943, for Low reflective elements, now abandoned. The invention relates to elements made of glass or the like and provided with a low reflective illm or coating on the part of its surface normally presented 'to an observer. Such a low refiective element is disclosed and claimed in a copending application of VFederick H. Nicoil, Ser. No. 461,958, filed October 14, 1942, and assigned to the same assignee as the present application. In accordance with this copending application, the glass surface is treated with dilute hydrofluoric acid vapor under conditions promoting substantially uniform gas concentration and `distribution at the treated surface, the treated surface being maintained at a temperature higher than that of the acid solu- -tion in order to prevent condensationof moisture at the treated surface, and thev treatment being continued until a layer skeletonized to the desired extent and having the desired thickness' is formed.

While the m thod of treatment disclosed by the aforesaid application has proved satisfactory in many respects, the necessity of maintaining a temperature difference between the treated surface and hydrofluori'c acid bath or solution is a commercial fluosiliclc acids treat the surface of a transparent body such as glass with vapor derived from a solution of fluosllicic acid while maintaining the silica number of the acid ait a value conducive to the production Aof a hard skeletonized fllm of low reflectance.

The invention will be better understood from .the following description when considered in connection with the accompanying drawings, .in which Figs.A l to 3 are cross-sectional views of three embodiments of an apparatus useful in practicing this invention;

Figs. 4a to 4d show time of treatment as a function of the assay and silica number of the acid;

Fig. 5 shows the assay and silica number of with relation to the desired characteristics for the treatment of glass;

Fig. 6 is a sketch illustrating a method of separating the reflections from the two surfaces of glass; Fig. '7 illustrates how variations in distance between the solution and the glass affect the time of treatment;

Fig. 8 illustrates .the relationship between 'the concentration of HzSiFe and the time of treatment;

complication which it is desirable to avoid. The

earlier method also involves rather exact control in order to insureuniform gas distribution and concentration at the surface undergoing treatment, and also to insure conditions suitable for the formation of hard films.

The present invention has for its principal object the provision of an improved method of operation which avoids the necessity of maintaining a fixed temperature difference between the treated surface andthe solution from which the active components are derived.

Another object is the provision of an improved method of operation whereby the concentration and distribution of the active sas is rendered more uniform, and the conditions for hard film formation are made less critical.

A further object is the production of a low reflective coating which is harder than those .produced by former methodsand requires less time for its production. n

A still further object of this invention is to Fig. 9 shows the linear relation existing-between the logarithm of the concentration and 'the logarithm of the time required to produce a quarter wave film;

Fig. 10 shows the logarithm of the time of treatment vs. the logarithm of the absolute temperature;

Fig. 11 illustrates the relation of film hardness to acid concentration;

Fig. 12 shows the film hardness as a function of the distance from solution to glass;

Fig. 13 shows the variation of hardness and time of treatment as a function of the amount of concentrated HF (47%) added to an original 16% solution of acid;

Fig. 14 shows the time of treatment vs. and

Fig. 15 shows time of ance of the glass.

Skeletonization as an aid to the reduction of reflection from a transparent body was first disclosed by Blodgett in Physical Review, February 15, 1939. A very thin film of soap was deposited on glass and the film was then treated to dissolve variation of hardness and the amount o'f added silica;

treatment vs. the reflectout certain components, leaving a skeletal structure with air filling the spaces formerly occupied by the dissolved material. Blodgett noted that the spaces and the solid portions must be of molecular dimensions. at least smaller than a Wavelength of light, if transparency is to be retained. Surface reflections are reduced by the well known interference effect when L.the lm thickness is equal to a quarter wavelength of the incident light. As is also well known, the maximum reduction of reflection occurs when the index of refraction of the film is equal to the square root of the index of the base glass, when viewed in air. The function of the skeletonlzation is to reduce .the index of refraction of the soap film to an approximation of the optimum value. This method has not come into commercial use because the film is extremely fragile and is easily wiped y olf.

The production of a reflection reducing film by the chemical treatment of the glass surface with an acid solution is also well known. For example, the glass may be immersed in a nitric acid solution. (See U. S. Patent 2,220,862.)A This method, however, is limited to the treatment of certain types of glass which contain a metal, and such glasses inherently have a high index of refraction. The nitric acid process is known as etching" and is distinguished from skeletonizing in that in the former case the acid removes only the metallic components of the glass and leaves a surface presumably of solid silica, since in every case the measured index of refraction -which results is simply that of solid silica; whereas in the latter case the acid reacts to some extent on the silica as well as the non-silicious components to produce a surface layer which has a porous structure of molecular dimensions characterized by an index of refraction which may be much lower than that of any component of the glass in its solid state. Also to be distinguished from skeletonizing are the various frosting processes which treat the interior of glass bulbs, for example. to produce a frosted or opaque surface which disperses the light. Frosting has no utility in the reduction of reflection since the transparency of the glass is destroyed. Frosting merely pits the surface. with no attempt to produce a surface film having a critical thickness bearing a predetermined relation to a wavelength of light, and since light is dispersed, the dimensions of the surface irregularities Amust be greater than a wavelength of light.

In accordance with the present invention it has been discovered that by substituting fiuosil'licic acid (HzSiFe) for the hydrofiuoric acid of the earlier' Nicoll vapor method, the necessity of maintaining a temperature difference between the solution and the treated surface is avoided. In addition to greatly simplifying the apparatus required, a coating of superior hardness is obtained. y

Glass in contact with saturated water vapor is known to have a thin film of water adsorbed on its surface. Asoluble, so-called iwhite deposit is formed during the production of the skeletonized film by the hydrofiuoric acid vapor method. This deposit consists of fiuorides and fiuosilicates. Also, water is a product of the reaction between the glass and hydrogen fluoride. These facts indicate that during the film formation a thin solution, saturated with respect to alkali and alkaline earth fiuorides and fiuosi'licates, exists at the glass surface, while an inch or two below the glass is a dilute hydroiiuoric acid solution.

Raoults law states that the vapor pressure of a solution is lowered in proportion to the molecular concentration of the solute dissolved. It is therefore apparent that the solution on the surface of the glass during treatment will have a lower vapor pressure than pure water at the same temperature due to the dissolved fiuosillcates. If the acid solution and the glass were maintained at the same temperature there would be a vapor flow in the direction of the glass tending to increase the water content in the solution on the glass surface. This is due to the'diiference in vapor pressures. Such a variation in water content on the glass surface produces a soft film or no film at all. The unequal vapor pressures have heretofore been compensated by Y decreasing the temperature of the acid solution to a value a few degrees below that of the glass. This result could be equally well produced by applying Raoults law to the acidsolution thus reducing .the vapor pressure of the solution to the desired value by the addition of salts, as described and claimed in a copending application of Nicoll and Williams, Ser. No. 488,938, filed May 28, 1943. If the salt solution on the glass is to remain approximately constant with respect to time it is necessary for the vapor pressure of the acid solution and the solution on the glass to be approximately the same. Under these conditions the glass will neither become wetter nor dryer as the process of film formation proceeds, and hence the best conditions for operation are maintained. In fact, it would seem advisable to select the conditions such that the solution on the glass surface would have a slightly greater vapory pressure so that some of the water formed during the glass attack would be removed.

The use of fluosilicic acid as a source of vapor for producing low-reflection films on glass came about as a result of considerations regarding the formation of fluosilicates and the silica film at the glass surface. The reactions occurring at the glass surface may be written in the following Way:

each molecule of metal oxide present. The silica which remains will form the skeletonized film if the second reaction does not proceed towards the right. The rate of silica lm formation will vary directly `as the first reaction and inversely as the second. It is therefore desirable to promote the first reaction and inhibit the second. On the basis of the Mass Action Law, the second reaction can b e inhibited by increasing the vapor pressure of SiF4 in the system. This mechanism may explain why increasing the HF vapor pressure too much fails to increase the speed of film formation and may even result in no production at all. 'Ihis would probably not be the case if the SiF4 vapor increased with the HF.

-The present invention may be practiced by filling a wax-lined copper tray i0, 2" deep by 12" square, with 16% iluosilicic acid I2 to a depth of Va". 'I'he glass I3 to be treated is then placed over the top of the tray preferably with an airtight seal around the edges and covered with a copper plate or lid Il. At a temperature of about vsinned for the purposes of this discussion 25 C. there is produced in about 41/2 hours a hard low index film of a thickness suitable for minimizing the reflection of green light. A coating of ceresine wax is used in the tray to prevent attack by the acid, or it can be coated with several baked layers of Harvel 612C insulating varnish made by the Irvington Company of Irvington, New Jersey. Metal is specified for the tray i and lid il because of its thermal conductivity. The conductivity of the tray and lid assists greatly in maintaining temperature uniformity of the glass and solution. While it may not be essential to use metal when the temperature stability of the room is particularly good, there is always a certain amount of dangerfrom drafts causing non-uniformity of temperature over the glass surface. This is the reason for recommending the use of metal trays and covers except under conditions that are exceptionally suitable.

Referring to Fig. 2, an alternative arrangement is shown for eliminating drafts and unequal temperature. It will be seen that/the tray I0 is lined, is provided with the acid solution i2, and is covered by the glass I3 to be treated. In these respects the apparatus of Fig. 2 is similar to that of Fig. 1. The copper plate Il of Fig. 1 is replaced by an inverted tray or lid I1, which is preferably made of metal, and which traps the air in an enclosed space so as to eliminate air currents and maintain a uniform temperature distribution.

When several small pieces ofglass are to be treated, the apparatus of Fig. 3 may be used. In this arrangement the tray I0 is covered by a metal plate I8 which is provided with openings I8. The openings are adapted to receive the glass pieces to be treated. The several pieces 20 may be supported by nne wires 2|. The suD- porting wires may be soldered or otherwise fastened to the metal plate. This method of treating small pieces has been found to give uniform films to within 11s" of the edge of the treated surface.

The fiuosilicic acid solution is made up from technical quality concentrated acid (usually 30%) althoughcommercial quality may be satisfactory. A concentration of 16 percent by weight is used in general, but as much as percent may be used on some glasses in order to speed up the process. It has been discovered that the HF content of the acid is to a large extent the determining factor in the operation of the process, and for best operation the composition of the solution in th'e tray must be kept within certain limits, to produce acceptable low-reflection films. The raw acid from various sources shows considerable variation in composition. Even from a single source, the composition cannot be relied upon to'remain constant. The tray solution is found to change slowly in composition while it is inservice, presumably because of evaporation and reaction with glass.

Thus it is evident that a method of fully characterizing and controlling the composition of fluosiiicic acid solutions may be useful in the vapor process of treating glass. Such a method h'as been developed by S. M. Thomsen. It consists of two acidimetric titrations on the sample. Procedures for these titrations will be given, together with control operations based on the results of the titrations.

The ordinary fluosilicic acid is generally specifled as vbeing This is a percentage by weight. These percentage figures will be abanfor two reasons. First, while a pound of 30% acid diluted with a pound of water yields a 15% acid, if the 30% acid is diluted instead with an equal volume of water the resulting solution is over 16 Second. two solutions may both be 16%, and yet differ in composition, because'the acid can vary in silica content. Therefore, the assay will be defined as what might be called the total acidity, as obtained from the titration II to be described, computed to moles per liter of HzSiFn, assuming 6 equivalents of alkali per mole of HzSiFe. This figure, M, is independent of the silica content, and dilution with an equal volume of water reduces the assay (so defined) or molarity, to half. Commercial 30% acid has ranged from 2.5 to 3.1 molar (moles per liter of HzSiFs) Unlike most acids, fiuorsilicic acid varies in composition aside from its water content. Specifically, the silica content may be less or greater than that demanded by the formula HzSiFs. The silica content may be specified as a silica number, S, so defined in terms of titrations I and 1I, that for the theoretical HzSiFe the number is 1.00, and the number is proportional to silica content. Fluosilicic acid in concentrations near 2.5 molar, lfully saturated with silica, has a silica number of 1.18. That is, it contains 18% more silica than the theoretical HzSiFa. Hydrofiuoric acid, HF, may be considered to be fluorsilicic acid of silica number 0, since it contains no silica. Consequently, a silica number of less than 1.00 means the presence of free HF. Commercial 30% acid from various sources has ranged from 1.03 to 1.18 in silica number.

It should be understood that the silica content consists not of free silica, but of fluorinated species such as SiFs=', HzSiFs and probably SiF4.

If the vigor of the attack on theglass by the tray solution is too great, a soft film results. If too low, the resulting film is too high in index, and therefore too low in efllciency. The greater the concentration (assay) and the lower the silica number, the more vigorous the attack. At certain combinations of assay and silica number, therefore, a particular glass will produce a film which will be a chosen compromise between hardness and emciency. Treating time for a particular'glass at a particular temperature is determined by the composition of the solution. As seen from the curves for four sheet glasses in Fig. 4, hardness and treating time increase upward and to the left in each case. The dotted line connects combinations which produce films of about the minimum hardness acceptable as judged by a fingernail test, and these films are near the optimum index of refraction, and therefore rather efficient. These data were obtained with a distance from solution to glass. Trays of other dimensions may be expected to display a shift in the values required to produce a given result; deeper trays require more vigorous solutions.

Since' it has not previously been known that the silica content of fuorsilicic acid varies conin the tray process, a 5.00 ml. sample is taken mality N (2 to 2.5).

7 for analysis. It is delivered from an internally waxed pipette into a Lucite dish.y About 3 gm. (r0.5 gm.) oi' powdered NaF is added. Lumps generally form; these are broken up with a Bakelite rod, and the mixture stirred. Bromthymol blue indicator, l drops of 0.1% solution in alcohol, is added, making the mixture a bright yellow. Thel mixture is titrated with NaOH of nor- At the approach of the end point, the color becomes greenish yellow. The end point is taken at the darkening to a blue of greenish cast. Running past the end point produces a royal blue; this color cannot be used for the end point,- because while it appears with each added drop of alkali, it soon fades to the greenish bluev mentioned. Care must be taken to titrate the acid trapped among the solid particles; the yellow or yellow-green must not return upon stirring. If some of the alkali is run in before the NaF is added, softer lumps or none are formed, and the titration is done more quickly. Let A=No. of mi. of NaOH solution consumed. Titration II is performed as a further operation on the same sample.

This is the usual assay titration described in the literature. The blue mixture left after titration I, about ml. in volume, is washed into a 600 mi. Pyrex beaker with hot (95 C.) water, and the volume brought to about 300 ml. The solution is now greenish yellow in color. Phenolphthalein indicator (10 drops of 1% solution in alcohol) is added and titration with NaOH continued. The solution darkens throughgreen to blue as the end point is approached. The end point is taken as the phenolphthalein turns red; and since this is mixed with the blue of the first indicator, the end point is the appearance of a purple color. The solution is nally brought to 95 C. and stirred; if the 'purple color does not fade to blue the titration is completed. Let B=No. of ml. of NaOH solution consumed by the sample, including that used in titration I.

Titration of a 5.00 ml. sample yields the following data:

N-normality of NaOH A-mL NaOH, titration I B-ml. NaOH, titrations II-i-I The assay or titre, M, is then M=%BN 1%) The titration ratio, is dened as R=A/B from which the silica number, S, is given by S=3/2 (l-R) (1i-005) Designating asMo, So, the composition of the raw acid on hand, or the solution to be adjusted, and as Mx, SKA, the composition to be achieved, the computation will be separated into several steps to avoid complications.

A. Dilution to 2.50 molar. Take Vo ml. of the solution of composition Mu, So, and add water to make the volume V1:

, :m The volume of water required W1 will be W1=V1Vo B. Decrease of silica content (if required) from So to Sx. To the V1 ml. of acid (M=2.50, S=S0) add F ml. of 15 N HF as follows:

This makes the volume now V2 ml.:

of fluosilicic acid, M=2.50, S=Sa D. Final dilution from M :2.50 to Mx. To the V2 ml. of acid (M=2.50, S=S1), water is added to increase the volume to Va, thus:

2. VF( Vl The amount of water required is W2 ml., thus:

W2=V3V2 The nal result is V3 mi. of acid, M :Ma S=Sz, obtained by adding to Vn ml. of the original acid W ml. (=W1+W2) ml. of water and either F ml. of 15 N HF or W ml. of silica saturated 2.5 molar acid.

These reagents were chosen to have the same assay (by titration II) as the acid (2.50 molar) with which they are to be mixed, to simplify computaticns.

The required 15 N HF is obtained by diluting a concentrated acid of known titre. The titre is obtained by the conventional titration (using plastic or waxed containers) with NaOH (aboutI 22.5 normal) using phenolphthalein indicator. Thus, for a, 5.00 ml. sample, consuming M ml, of NaOH of normality N, the titre T (normality) of .the HF is as follows:

This reagent may be thought of as 2.50 M fluosiliclc acid from which all of the silica had been removed (silica number :0)

The 48% C. P. hydrouoric acid has been found to run close to T=28 normal, and, if this value is assumed, 15 N acid may be prepared by diluting ml. of the 48% acid with 130 ml. of water, giving a volume of 280 ml. of 15 normal HF.

The 2.50 molar silica saturated uosilicic acid is prepared by suspending hydrated silica in a 2.50 molar iluosilicic acid solution for several hours, agitating occasionally and ltering. Crude silica (powdered sand) dissolves too slowly to be usable.

Fig. 5 is a graph showing (a) the assay (Mo) and silica number (So) of 4 samples of commercial 30% HzSiFe as received from the manufacturers. "ample A has a molarity of over 3.0 and a silica content approaching saturation (1.185). Without correction the vapor from this acid would not skeletonize glass. Samples B and C are about the same, M is approximately 2.8 and S is 1.10. From the curves of Fig. 4 it may be seen that without correction as to silica number 9 a film of h igh index would result. and tbe silica number preferably should be reduced to a more suitable value as described above. 'l'.'he coincidence of these samples having'nearly the correct silica number explains why skeleton films were produced with these acids. Dilution alone would bring these samples into the region which would produce a usable nlm on certain glasses. Sample D is on the upper edge as to strength but too low in silica number. This results in excessive activity and a soft film is produced.

Another method of determining whether a given sample of acid is suitable is to conduct a series of tests using small cups approximately 2 in. in diameter and large tray. 16 percent solutions of the acid are made up and various small quantities of silica are added to another range of samples. A good range to cover in such trial samples is from to l percent HF and from 0 to 100 mg. of powdered silica per cc. of 16 percent solution. About five equal steps for both sets of samples is most suitable and these should suffice for the commercial acids available. These sample cups are now used to produce a film on the particular glass which it is desired to treat, the glass being placed on the top of the cup. After a period of ten hours or soa number of the cups will have produced films and if they have been observed periodically it will have been possible to remove all the samples at or near the first minimum of reflection. The results will now show a variation of the same depth as the' in time of treatment, hardness, and the efficiency of the reduction of reflection. It is necessary at this point to select the most suitable result an-d note the solution which produces it. The best sample consists of a compromise of the abovementioned factors but it is essential to obtain low reflection, at most 10 percent of the untreated reflection, and yet retain a fair. degree of hardness. A hardness corresponding to about 8 x good results strokes with wet rouge using the arrangement described in a later paragraph on hardness is probably the minimum ,that should be considered. The quality of the selected film should be such that there is very little scattered light under fairly intense illumination against a'dark background. When the correct composition of the acid has been decided upon, a quantity of solution is made up sufficient to cover the bottom of the tray to a depth of about 1A; inch. If the tray is deeper than 1% in. then the acid is poured in till the distance from the acid to the glass 15.11/2 in. T'his is the recommended distance between glass and acid for the most satisfactory results.

It is, of course, necessary to maintain losses due to evaporation and when large quantities of glass are being treated it is necessary to replenish the solution due to the loss of acid in treating the glass. The need for this will become apparent when the'treating time has changed by about 10 to 20 percent. Because of the low vapor pressure of HF and SiF4 compared with the vapor pressure of H2O, the solutions tend to concentrate themselves so that water must be added as evaporation takes place.

As the treatment proceeds a white deposit forms on the glass which gives it a translucent appearance. The amount is a function of the glass composition. ,This must be washed off soon after the glass is removed from the tray, otherwise it remains strongly adhered to the glass.

The time at whichv glass of a given composition should be removed can be determined by inspec- `duce reflection is essentially tion after a little experience. In order to do this it is necessary to observe the color of white light reflected from the lower surface of the glass as it is exposed on the tray. This can be done by 0bserving the separate images from the top and bottom of the glass. Referring to Fig. 6. it can be seen that the images can be separated by looking at the shadow images of an opaque object Il. illuminated by the light source 23,'whichmay be any source such as an electric light bulb. As seen by the eye 24 the image of the opaque body is observed to have a black middle portion and a light edge on the sides nearer and farther from the observer. The width of this edge depends on the glass 25 thickness and viewingangle. The edge farther from the observer is colored by the light from the lower surface 26, and this is the edge for observing the amount of treatment. The white deposit modifies the color of the lower surface and it has been found that the edge which shows the color of the lower surface should appear blue to the eye when the glass is finished if the glass has the composition of ordinary window glass. If the white deposit is now washed off with running water angl the glass dried. the surface will then appear the desired purple color.

Borosilicate crowns and heavy lead glasses appear to have less white deposit in general and the are therefore at the minimum for green light when the color with the white deposit on is between purple and blue.

For many purposes the time of treatment can be obtained fairly well by timing and correctingv for any average temperature change, if experiments have already been run on the same type of glass. This assumes that the acid concentration remains constant. It must be remembered that are only obtained in the neighborhood cf 25 C. with acid concentrations near 16 percent. 'When a number of trays are used it is desirable to have exactly the same concentration of acid in each tray (preferably obtained by mixing). If the height of the glass above the acid is the same in each same temperature then inspection of one tray serves to give the time ofremoval for all. Estimation of the approximate time of treatment can be obtained from a knowledge of the time of treatment at a givenv temperature for the particular glass used.

Fluosilicic acid vapor treatment of glass -to rea surface treatment and success therefore depends on the condition of the glass surface. For this reason polished plate glass and fire polished, flat drawn window glass of the same composition nevertheless treat at somewhat different rates. A good, clean surface is essential for obtaining .uniform films free from scattered light. The surface must also be Y a cloth, after which the Bon Ami is washed off of this white deposit before it dries. The glass is then thoroughly dried with a clean cloth.

Abrief dip, up .to about 4 min. in 0.5 percent HF solution, followed by rinsing and drying will usually give a good clean surface if the glass is fairly clean and grease-free before dipping. Too long a dip will visibly etch the glass and ruin the surface. This procedure window glass and is not recommended for polished glass. With fresh 'glass this treatment may be successfully used to removeroller marks.

tray and they are all at the is -best applied. to

Treated glass readily vpicks up oil or grease from contact with' oily or greasy materials and this -tends 'itc remove its low-reflecting properties. In handling the glass it is advisable to avoid such contact and also to avoid lingering Ithe glass. During shipment the glass must be wrapped 'in paper which will not produce spots on the glass after long contact. Glassine envelopes seem to be satisfactory for .this purpose. The treated glass can be cleaned withV water and any nonabrasive soap, but care must be taken to remove all the soap from the glass before it is dried with a cloth. 'Ihe treated yglass can be cleaned with any of the common acids if desired. 'I'he description which has already been given of the method of producing low-reflection films by the use of iluosillcic acid has indicated its dependence on a number of factors. In order to produce satisfactory films it is desirable to know the eii'ect of the various factors on the yillxn formation. These effects have been investigated fairly exhaustively and the results are given in the following paragraphs.

Errrcr or TRAY Ann The area of the tray was a factor in the older hydroiluoric acidl vapor method of reducing the renection from glass. In going from a tray of six hundred square inches to three square inches, the time of treatment was increased by about two hundred percent. This eil'ect was probably due to convection effects brought about by the use of treated glass is proportionately larger onv the small Itrays.

l Erncr or TRAY Hncnr Because the diiIusion of the fluosiliclo acid vapor from the solution to .the glass is one of the rate-limiting processes in film formation, and because the rate of iiow of a substance lvaries inversely with the length of the path of flow; ift would be expected that increasing the distance from the surface of the acid solution'to the glass surface being treated would increase the time of treatment. Experimentally this is found rto be the case, as is shown in Fig. '7 for 25- percent by weight I-hSiFs. The data for this curve were taken on trays three square inches in area. This curve over the 'approximate height range of,2.5 cm. Ito 6 cm. applies to trays up to at least six hundred square inches in area. Above about six centimeters high, convection difli'culties appear in the case 'of the trays of larger area. Convection currents cause soft non-uniform fllms as well as pronounced changes in the rate of nlm formation. Soltion-to-glass distances less than 2.5 centimeters also result in poor films, when using pure iluosilicic acid. For .the range of. tray heights over which satisfactory lms are ob, tained, the time of treatment for Libbey-Owens- Ford flat-drawn glass vari with the solution-toglass distance as is shown in Fig. 7 for. 25 percentt HzSiFs. Other glasses or other conentmtfiime of iiuosilicic acidmay result in different absolute' .times of treatment, but the variation of time of' Errlcr or CoNcnNrnArroN The concentration of the uosilicic acid wed as a source of hydrogen fluoride and silicon .tetrafluoride gas ailects fboth the rate of the reaction and the quality of the resulting film. Theoretically this eiIect is due to two reasons. First, increasing the concentration of iiuosilicic acid results in a decrease in the vapor pressure of water because the vanor pressure of each constituent is proportional to its mole fraction. This decrease in the water vapor pressure decreases the amount of adsorbed water on the glass surface so that the resulting film is harder and no temperature diil'erence is required. Second, increasing the concentration of iiuosilicic acid increases the concentration in the vapor of hydrogen fluoride and silicon tetrailuoride independently. These substances each aiect the rate of film formation in different-ways. The increased amount of hydrogen fluoride present at the higher concentration produces a more rapid attack on the glass while the silicon tetrailuoride more eiliciently inhibits the attack on silica at higher concentrations. `Solutions of iluosilicic I acid concentration less than 13 percent by weight have la greater ratio of HF molecules to, SiF4 molecules in the vapor than that corresponding to HzSiFa, whereas solutions having a concentration greater than 13.3 percent have a smaller ratio of HF molecules to SiFl molecules in the vapor than that corresponding -to HaSiFs. Because of these varied eil'ects of fluosillcic acid concentration on the rate of lm formation, the

experimental dependence of rate of film formation on concentration follows no simple linear behavior but is lbest shown by Fig. 8.

It is possible to determine the order of the reaction involved in a process from the slope of the curve of concentration against time. The order of the reaction is given by n in the expression In the film forming process the concentration changes only slightly as the lm is formed, and so it is more convenient to obtain the order of the reaction from the relation between the time to complete a definite fraction of the reaction and the concentration. 'I'he order of the reaction n is given by the relation 1 To CTP-1 which is derived from the above expression. In the case of film formation T is the time to produce a skeletonized silica film 1A; wavelength thick. Taking logarithme of both sides of this equation, the linear relation of the logarithm of the concentration and the logarithm of the time of treatment shown` in Fig. 9 is explained. The slope of this curve is n-l, giving a value of 5/3 for n. If the process of iilm formation were a simple one, the order oi the reaction would be aumen 13 an integer. The simultaneous occurrence of side reactions. consecutive reactions. or opposing reactions with velocity constants of the same order of magnitude as the velocity constant of the main reaction are known to lead to deviations ot the order of the main reaction from an integer. Alsol ionic reactions are known to have velocities which are dependent on the concentrations of all the electrolytes in the solution whether they take part in the reaction or not. It is therefore most likely that the order of the reaction is represented by the nearest integer to that obtained from the slope of the curve. This indicates that the process of illm formation is a second order reaction, which means that the slowest step in the process of film formation involves two molecules of iluosilicic acid. A-possible mechanism satisiylng this requirement is shown by the equation:

Experimentally it has been found that below about per cent fluosllicic acid large droplets are prone to form on the glass because'of the high water vapor pressure. This produces soft films. Above about percent iluosilicic acid, the tendency is to form visible etching and crystals. Crystal formation is particularly apt tooccur when high iiuosilicic acid concentrationvis coupled with high temperature. The limits of concentration vover which satisfactory results are Errlcr or Tnurnnams Small temperature changes produce quite large effects on the time of treatment. At 25 C.; for example, 10 percent decrease in time of treatment, while a temperature drop of 1 C. results in a 10 percent increase in the timeoi' treatment. The temperature Vdependence of time of treatment is shown in Fig. 10 for 16 percent and 25 percent iluosilicic acid over the temperature range of 0 C. to C. At .both concentrations the curve of the log of the time of treatment plotted against the reciprocal of the absolute temperature approximates a straight line. This indicates that a temperature rise of 1 C. results in a the heat of Vactivation for the rate-limiting process is only slightly temperature dependent. Also, the curves for the 16 per cent and the 25 per cent fiuosilicic acid being parallel indicatesthat the heat of activation is only slightly dependent on concentration over this range. From the slope of the curve, the heat of activation can be calculated from the formula:

4Lor` 12-14 o. window' is more than compensated by the inconvenience of operation.

Dnraxmnecr: or Haammss on Vaarous Facrons Table i Glass Process Hardness M in. Pittsburgh platew.. LOF 12-14 oz. window 16% Hisir. .do

..do -..do

Ethylene glycol and HF.

1% HF with temp. dim...

L F 12-14 oz. window glass.

These results were obtained on a 1/2 in. deep tray using 16 percent HaSiFa and were determined by measuring the number of polishing strokes necessary to remove the illm using a felt pad and rouge. A weight of 380 gms. was used to press a cork-backed felt pad onto the glass. The pad was 1 in. in diameter and it was moved slowly back and forth by hand, the glass being wet with a mixture of rouge and water. Strokes were then counted as the pad moved forward or backward until the film was fairly well removed. These measurements give satisfactory results when used on the same typev of 111m but are not so good when comparing films of different structures. The measurements of Table 1 were made with 16 percent HzSiFs at 25' C. using a tray with solution-to-glass distance of 3.5 cm.

In general, the hardness of the illm seems to be greater the longer the time of treatment. This fact is exempliiled by the curves of hardness vs. concentration and hardness vs. tray depth which are shown in Figs. 11 and 12, respectively. These results were obtained using the felt pad and rouge polishing method. I'he curve for varying concentrations was obtained on 5.3 cm. diameter cups for a heightof 2 inches using Libbey-Owens-Ford meter glass. The results for varyingheight were obtained on similar glass and cups using `an acid concentration of 24 percent. It can be seen from the results that it is essential to arrive at a compromise between hardness and time of treatment. This we believe is best reachedvby using a tray 11/2 in. deep with a concentration of 16 per cent.

All the results described so far have been obtained by the use of fiuosilicic acid in which the HF and SiFl are present in solution corresponding to the composition of HzSiFa. It was soon found that not all commercial iluosilicic acid would produce ya satisfactory film on glass. Owing to different methods of preparation, some of the acid had too little HF in it. in other words an excess of silica (most probably as SiFi) while othermakes of acid had too much HF. Experiments showed that both these makes of acid could be made to work satisfactorily by adding suflflcient HF or silica to bring the HF concentration back to the correct working value. Time oi treatment, hardness, and the index of the illm are all dependent on the HF content. It has been pointed out earlier, in the procedure for treating must be added is to do a series glass with fluosilicic acid, that the best method of determining the quantity of silica or HF that of experiments in small cups.

Fig. 13 shows the results of such a series of experiments on Du Pont commercial fluosilicic acid. Two approximately straight lines show the relation of hardness and times of treatment as a function of the amount of concentrated HF (47%) added to the 16 percent solution of Du Pont acid. These results are for Libbey-Owens- Ford window glass. As the HF content increases the hardness decreases and the time of treatment decreases. When about 2.5 percent HF has been added the hardness and the time of treatment are approximately the same"as we would get if we had used 16 percent C. P. Baker uosilicic acid with no HF added. The Du Pont acid therefore had the equivalent of about 2.5 percent negative HF. For low values of the HF content where the time of treatment is long and the film is very hard the index of the nlm is relatively high and the reduction in reflection is not very great. This corresponds to a silica film which is only slightly skeletonized or in whichv the skeleton is filled up with some material of greater index than air. For high-values of HF content the process is much more rapid but the iilm is soft.

Fig. 14 shows the results obtained by adding various amounts of silica to C. P. Baker uosiiicic acid. These results fit in with those just described, and time of treatment and hardness increases with increasing amounts of silica. The index of the film also increases with the addition of silica to the acid solution. The results are for Libbey-Owens-Ford -window glass. Time of treatment is given by the continuous curve and the dotted line gives the results for hardness.

It has been mentioned earlier that satisfactory films could never be obtained at solution-toglass heights less than 1 inch when using 16 percent iiuosilicic acid. In fact it was observed that experimentally it Was not possible to obtain good lms at lower heights even with other concentrations. In the experiments on adding silica to Baker acid it was found that the addition of silica in small quantities made it possible to obtain satisfactory lms at heights as low as onequarter inch. It was also found that although concentrations of Baker C. P. acid greater than 25 percent would not produce satisfactory lms, the addition of silica made it possible to use concentrations as great as are available, viz. 30 percent. Due to the addition of silica, however, the time` of treatment was still relatively long.

The above experiments indicate the important role that is played by the HF in the iiuosilicic acid solution. The correct quantity is best determined by experiment and in general it has been found that the best results on the majority of common glasses are obtained when the HF content corresponds quite closely to that present in pure HzSiFs.. In addition it seems most desirable to use a tray height of 1 1/2 inches and a treating time not less than about four hours at 25 C.

EFFECT or GLAss COMPOSITION AND TYPE The fiuosilicic acid vapor process has been used to treat a large number of glasses ranging from crowns to heavy fiints. Time of treatment is a function ofthe composition of the glass and Table 2 gives the time of treatment of a number of different glasses, some of which are rouge polished and some are fire polished.

Table 2 Approximate relative treating times of various glasses. 16% HiBiF, 25 C., tray l2 x `12 in., glass to liqu d 1% in.)

4lirne to ist Glass Minimum in Minutes X-ray protection glass, polished 110 Barium flint, polished 215 Dense barium crown, olished 225 Borosiiicate crown, po ished 240 L. 0. F. 12-14 oz. picture glass, ill'elolishedA 240 M in. Pittsburgh plate, polished an herculit 240 L. O. F. single strength, fire polished 240 L. 0. F. double strength, lire polished 270 is in. Pittsburgh plate polished. 270 56 in. L. O. F. plate. po ished. 270 54 in. Pittsburgh plate, Polish 270 M in. L. plate, po lshed. 270 Spectacle crown. xpolish 270 Dense flint, pol ed 280 is in. Pittsburgh window glass, fire polished. 415

The conditions under which the results were obtained are given at the top of the table. It can be seen that X-ray glass treats the most quickly and Pittsburgh window glass the most slowly. This latter glass is very similar in composition to the other Window glasses but the annealing process is so different that the treating time is greatly affected. Pyrex cannot be considered as e treating satisfactorily although some samples have given films under special conditions in about 19 hours. Fused, polished silica has never given a satisfactory film and in fact has shown no evidence of any film whatever.

THIcxNsss-Tmn RELATIONS Fig. 15 shows the relation betwen time of treatment and the measured reflection of the glass. The reflection was measured by the combination of a tungsten light source having negligible emission in the violet and a 929 photocell having negligible sensitivity in the red. This arrangement is most sensitive to the green and corresponds to the eye sensitivity. The colors recorded along the curve are those observed visually after the white deposit has been removed. This curve indicates that a time variation of about 6 percent may be allowed from one piece to another without varying the reflection of the finished glass by too large an amount. This, of course, assumes that the concentration remains constant, and also the temperature.

What we claim is: Y

1. The method of reducing the index of refraction of a glass surface with an acid vapor derived from a uosllicic acid solution having between 3% and 10% by weight more silica than called for by the theoretical proportions of the formula HzSiFs, which includes the step of subjecting a surface of said glass to said vapor, while maintainingsaid glass and said vapor at substantially the same temperature. v

2. The method of reducing the index of refraction of a glass surface with an acid vapor derived from a fluosiliclc acid solution having between 3% and4 10% by weight more silica than called for by the theoretical proportions of the formula HzSiFs, and a molarity between 1 and 2.5, which includes the step of subjecting a surface of said glass to said vapor, while maintaining said glass and said vapor at substantially the same temperature;

3. The method of reducing the index of refraction of a glass surface with an acid vapor derived from a uosilicic acid solution having between 3% and 10% by weight more silica than called for by the theoretical proportions of the formula HzSiF, and a molarity between 1 and 2.5, which includes the steps of exposing a surface of said glass to'vapor emanating from said solution in a substantially air-tight container. maintaining a uniform distance at all points on said surface between said surface and said solution, maintaining said glass and said' solution at substantially the same temperature, and continuing said exposure until the index of refraction of said surface has been substantially reduced.

4. The method of reducing the index of refraction of a glass surface which comprises treating said surface with iiuosilicic acid vapor equivalent to that existing in a closed chamber at a distance approximately 11/2 inches from an aqueoussolution of fiuosilicic acid having a molarity between 1 and 2.5 and a silica number between 1.03 and 1.10, and continuing said treatment until a purple interference color is observed when said surface is viewed inv white light.

5. The method of producing a low reilection transparent surface on glass which includes the step of skeletonizing a surface layer of said glass to a depth approximating a quarter wavelength of a component of visible light, or an odd integral multiple thereof, with gas emanated from a solution of uosilicie acid having a molarity between the approximate limits of 1 and 2.5 and a silica number between the approximate limits of 1.03 and 1.10 while maintaining said glass and said solution at approximately room temperature and continuing said skeletonlzation until the index of refraction of saidsuriace is of the order of the square root of the index of refraction of the untreated glass. s

6. The method set forth in claim 5 which includes the additional step of maintaining a 11/2 inch spacing between the surface of said glass and said solution.

'1. The method of producing a low reflection transparent surface on glass by means of vapor emanated from a solution of uosilicic acid which comprises adjusting the concentration of said solution to a molarity between the approximate limits of 1 and 2.5, adjusting the silica number of said solution to a value between the approximate limits of 1.03 to 1.10, exposing said glass to the vapor emanated from said solution in the absence of circulating air. and continuing said exposure until a purple interference color is observed when said surface is observed in white ligh FREDERICK H. NICOLL. FERD E. WILLIAMS.

REFERENCES CITED The following references are of record in the fue of this patent:

UNITED STATES PATENTS Number Name Date 254,263 Bitterlin Feb. 28, 1882 1,565,869 Straw Dec. 15, 1925 2,215,039 Hood Sept. 17, 1940 2,337,460 French Dec. 21, 1943 2,410,300 Nicoli oct. 29, 1946 

